Process for preparation of silicone graft copolymerized fiber or cloth

ABSTRACT

A silicone graft copolymerized fiber or cloth is prepared by first dyeing the cloth with a dyestuff containing metal in the form of a complex salt, and then applying a silicone having a general formula of   WHEREIN R and R1 are hydrogen or alkyl radicals up to five carbon atoms and R and R1 can be the same or different, and n is an integer, to the dyed cloth and subjecting said silicone coated dyed cloth to an ionizing radiation wherein the dosage of said ionizing radiation is within a range of from 104 rad. to 107 rad.

United States Patent Inventors Priorities Toshizo Chitani;

Shikanosuke Yokoyama; Shinko Nishide, all of Tokyo, Japan July 10, 1967 Nov. 2, 1971 Hakuyosha Co., Ltd.;

Toshizo Chitani,

part interest to each July 18, 1966 Japan July 18, 1966, Japan, No. 41/415560; Nov. 2, 1966, Japan, No. 41/715154 PROCESS FOR PREPARATION OF SILICONE GRAFT COPOLYMERIZED FIBER OR CLOTH 5 Claims, No Drawings US. Cl 8/115.5, 8/115.6, 8/2, 8/17, 8/165, 117/9331, 204/l59.l3 Int-CI D061n 11/00, D06p 5/02 Field of Search 8/D1G. l,

DIG. 18,74,2,17, 18,1155; 117/9331; 204/l59.13

Primary Exam iner-George F. Lesmes Assistant Examinerlohn R. Miller An0rne vWenderoth, Lind & Ponack ABSTRACT: A silicone graft copolymerized fiber or cloth is prepared by first dyeing the cloth with a dyestuff containing metal in the form of a complex salt, and then applying a silicone having a general formula of H2000 l 000 --Si0 Li J.

1 wherein R and R are hydrogen or alkyl radicals up to live carbon atoms and R and R can be the same or different, and n is an integer, to the dyed cloth and subjecting said silicone coated dyed cloth to an ionizing radiation wherein the dosage of said ionizing radiation is within a range of from 10 rad. to 10 rad.

BACKGROUND OF THE INVENTION It has been known prior .to the invention that silicone grafted copolymer can. be made by applying silicone to fiber, thereafter subjecting to irradiation by ionizing radiation on the order of from about to 10 rad. However, in the known process, the degree of grafting is very low. For example, the degree of grafting is on the order of 2.4 percent by weight (silicone/fiber), even if silicone is applied to fiber in an amount of 100 percent by weight (silicone/fiber), and irradiation of 5X10 rad by ionizing radiation is used. In another example, the degree of grafting is on the order of 0.9 percent by weight (silicone/fiber), when silicone is applied to fiber in an amount of 5 percent by weight (silicone/fiber), which is the proportion generally adopted in industrial operations, and ionizing radia-.

tion is irradiated 4X10 rad. If the total dose of irradiation of ionizing radiation is increased to increase the degree of grafting, the tensile strengthof the fiber or cloth significantly decreases in proportion to the increase of total dose in irradiation. Accordingly, in practice, it is necessary to develop a process which carries out silicone graft polymerization efficiently using lower dose ofirradiation.

The process for graft copolymerizing silicone with a fiber is useful as a process for giving a water proof finish for a fiber,

since the copolymer obtained is water proof. However, in the known prior art, because of the low degree of grafting in the copolymerized fiber obtained, the durability of water proof-1 ness disappears after being subjected a few times to commercial drycleaning.

SUMMARY OF THE INVENTION In this invention, the inventors have overcome the deficiencies of known processes bythe thorough study ofthe processes-for preparing a silicone graft copolymerized fiber having a high degree of grafting and excellent durability of.

water proofness.

Accordingly, the primary object of the invention is to provide processes for preparing an improved silicone graft copolymerized fiber. Another object of this application is to,

provide improved processes for imparting a long lastingwater proof finish to cloth.

A further object of this invention .is to provide a silicone graft copolymerized fiber havinga high degree of grafting and long lasting water proofnesswhich could not be obtained by the prior processes. Other objects of. this invention will be apparent from the following disclosure and examples.

The improved processes for preparing a silicone graft copolymerized fiber provided by this invention include the following processes.

The first process for preparing a silicone graft copolymerized fiber comprises copolymerizing silicone with fiber by irradiating fiber and, silicone together with an ionizing, radiation, characterized in that said irradiation is carried-out:

under heating, This process reflects the inventors discovery that silicone graft copolymerized fiber having high degree of grafting and long lasting'water proofness can be obtained. when silicone is applied to fiber and subjected to irradiation.

by ionizing radiation under heating.

When silicone is applied to afiber or cloth, and then expose to radiation, silicone is copolymerized with fiber. However, in.

thereby producing a silicone graft copolymerized fiber or cloth which has excellent durability of water proofness.

As for the fibers utilizable in the process of this invention, natural, fiber, semisynthetic fiber and synthetic fiber and Wherein R and R are hydrogenor alkyl radicals having less than five (inclusive) carbon atoms and R and Rv can be the same ordiffeient, and n is an integer. Any suitable process such as impregnation, spraying or the like can be used for applying a silicone to the fiber or cloth. Also, in spraying or impregnation, water, methanol or other organic solvent can be used as a diluent for the silicone. If water'or acetone is used as the solvent, it is unnecessary to remove the solvent prior to the exposure to theirradiation. In fact, sometimes, the presence of such solvent increases theeffectiveness of the process.

Any of the ionizing radiations such as 'y-ray, X-ray, electron beam, proton beamor neutron beam etc. canbe usedin this process. The suitable total dose of the irradiation is within the range offrom l0 rad to l 0 rad. If the total dose ofirradiation is less than the above-mentionedtotal dose of irradiation, the degree of grafting is low and the desired result cannot be obtained. If the totalfdoseof irradiation is higher than the maximum above-mentioned, the properties of the treated fiber cloth change significantly, and the fiber ,cloth is not suitable for use.

In the process of thisinvention, it is necessary to carry out exposure to theirradiation while thefiber cloth is under heat.. The temperature of thefiber cloth must be kept below the temperaturethe fiber cloth treated by theiprocess can resist. For example, if the fiber treated in the. process is polyvinylchloride, the temperature is less than 60 C.; if thefiber is.

polyethylene, lessthan C;; if wool or polypropylene, less than ",C.; cotton, vinylidene, nylon, less than C.; less than 1703C. for. silk, and when rayon,.cupra, acetate, Vinylon, polyester, or polyacrylurea, the temperature is less than 200 C.

In the process of this invention, thetreatment is complete aftersubjecting the article to irradiationv under heated condition, However,- if further heating is applied followingirradiation, amore. favorable result can be obtained.

A silicone graft copolymerized fiber obtained by the present process and the silicone graft copolymerized fiber obtained by the known priorprocesses were subjected to extraction using a solvent having ability to dissolve siliconesuch as petroleum benzine, and the respective degree of grafting compared. The degree of grafting of silicone copolymer obtained by a known process usi'nga fabric on which silicone was applied on the. order of 5 pericentand irradiation of 4.0Xl0 rad was only in the order of 0.92 percent; contrary to this, the degreeof grafting of silicone copolymerized fiber obtained by this process (ie which was irradiated of only 2.6Xl0 rad and heating to 80 C. was increased to 1,62 percent. Although total dose of irradiationwas decreased to about 65 percent of the known process, the degree of grafting increased about 8,0 percent. Also, when water repellent test is made in accordance with the provision of ASTM; D583-5 8, it was found that water repellent rating of the product treated by the known prior process using 4.O l0 rad of irradiation decreased to water repellent rating 50 after 7 commercial drycleanings, on the other hand,

water repellency ofthe product treated by the present process using 2.6 l0 rad of irradiation decreased to rating 70. It is apparent that inmaintaining water proofness of the product obtained by this process is far superior (70) to that of prior art (5O).

The second process of this invention is a process for preparing a silicone graft copolymerized fiber which comprises copolymerizing silicone with a fiber or cloth by irradiation of the silicone and fiber, together with an ionizing radiation, characterized in that the fiber is dyed with a metaLcontaining dyestuff, silicone is thereafter applied to the dyed fiber, and the fiber then being subjected to an ionizing radiation. This process reflects the inventors discovery that in the preparation of silicone graft copolymerized fiber, it was found if a fiber dyed with a metal-containing dyestuff is used as the fiber to be treated, graft copolymerization takes place effectively, and even if low total dose of irradiation is used, the degree of grafting is high, resulting in a silicone graft copolymer having excellent durability of water proofness.

In general, it is seldom that the water proof finish is given to white (undyed) cloth, usually, the water proof finish is given after dyeing. Accordingly, it is very advantageous if a good graft copolymerized fiber can be obtained using metal-com taining dyestuffwhen dyeing is carried out.

All the fibers shown as utilizable in the first process of this application can be treated successfully by this second process.

Any of mono-azo dyestuffs, poly-azo dyestuffs and phthalocyanine dyestuffs are utilizable in this process, provided that they are metal-containing dyestuffs. In short, any dyestuff contains metal in its molecular structure can be used. It is preferable that the dyestuff contains the metal in the form of complex salt, since in this form the dyestuff has good efficiency even if a low irradiation dose is used. Further, any of dyeing processes generally used in the art can be used in this process. The degree of grafting, of course, varies in accordance with the concentration of the dyestuff, but in any event, the grafting rate is increased by use ofthis process.

Further, the silicone employed, the process for applying said silicone to the fiber cloth, the kind of radiation used and the total dosage of the irradiation are substantially the same as in the first process. In the process of this invention, after being irradiated, the finished article can be used without further processing; however in practice, it is preferable to heat again after the irradiation.

The silicone graft copolymerized fiber or cloth obtained in accordance with this process is, like that obtained in accordance with the first process, far superior in durability of water proofness and has a higher degree of grafting than that obtained by the known prior process.

The third process of this application is a process for preparing a fiber cloth incorporating a graft copolymer of silicone with thermosetting resin or thermoplastic resin characterized by applying a thermosetting resin or thermoplastic resin and silicone to fiber cloth, and subjecting the combination to irradiation by an ionizing radiation.

In the silicone graft copolymerized fiber cloth obtained by the known prior processes in which silicone only is grafted to the fiber cloth, the fiber cloth becomes slippery if the quantity of silicone added is increased beyond a certain point. However, in the process of this invention the silicone is grafted onto the fiber cloth in the presence of a thermosetting resin or thermoplastic resin and the processed fiber cloth retains both stiffness and softness to give a superior feel." Further, the water proofness of the finished article is maintained significantly longer.

The same fiber cloth in the first process of this invention, can be used in this (the third) process. Further, the process is especially suitable for use with natural fiber and gives significant effect.

Any of the thermosetting resin and thermoplastic resins which are generally used for fiber cloth finish, such as melamine resin, urea resin, ethylene urea resin, acrylate resin or the like, can be used in this process, but a thermosetting resin is preferable. A fiber cloth incorporating a graft copolymer of silicone with a thermosetting resin retains its water proofness for an especially long time and is excellent for water proof finished fiber cloth. Any of the silicones mentioned in the first process of this invention can be used in this process. As for the process for applying the thermosetting resin, thermoplastic resin and silicone to the fiber cloth, any suitable process such as impregnation, spraying or the like, can be used. Further, it is possible to add an inorganic salt catalyst, organic amine catalyst to the treating solution, if it is desired to do so.

The kind of irradiation utilizable in this process and the total dose thereof are the same as in the first process of this application. In this process also, the finished article, after being irradiated, can be used without further processing; however, in practice, it is preferable to apply heat again after irradiation.

When a fiber cloth treated in accordance with this process is subjected to an extraction using petroleum benzine which has the ability to dissolve silicone as a solvent, it shows a weight increase in the same order or more than silicone copolymerized fiber. Above weight increase is calculated as follows:

weight increase (weight of grafted silicone) weight after extracted (weight of fiber weight of resin) From the data above, it is apparent that not only is silicone added, but a fiber cloth incorporating a graft copolymer of silicone with thermosetting resin or thermoplastic resin is produced. Also, when tested for water repellency in accordance with the provisions of ASTM; D-583-58, it was found that water repellency of the cloth treated by the known prior process survived only few drycleanings, however, the cloth treated by this process retained a repellent rating of even after more than 15 commercial drycleanings. It is recognized that the durability of water proofness is significantly increased by the treatment of this process. Incidentally, the commercial drycleaning test was carried out using the following apparatus and conditions:

inside diameter of apparatus l m.

number of revolutions per min. 4] r.p.m liquor ratio Kl cleaning solution solvent Industrial gasoline No.5 or JIS K 221M detergent polyoxyethylene ulkyl ester type 9.72; petroleum sulionate type 4 l .74'1 detergent concentration I; time for cleaning 30 mm. rinse (solvent without addition ofdetcrgentl IU min.

The above, three processes impart excellent characteristics respectively. It is also possible to combine the processes arbitrarily. By combining these processes suitably according to the object desired, a silicone graft copolymerized fiber cloth or a fiber cloth incorporating graft copolymer of silicone with thermosetting or thermoplastic resin and which is more suitable to the desired object can be obtained.

Accordingly, other processes ofthis invention are any combination of processes No. l, 2 and 3 for preparing a silicone graft copolymerized fiber or a fiber incorporating copolymer of silicone with thermosetting or thermoplastic resin according to this invention. That is, the processes include a process for preparing a silicone graft copolymerized fiber cloth characterized by applying silicone to a fiber cloth which has been dyed with a metal-containing dyestuff, thereafter subjecting said treated fiber cloth to irradiation by an ionizing radiation under heating; a process for preparing a fiber cloth incorporating a graft copolymer of silicone with thermosetting or thermoplastic resin characterized by applying the thermosetting or thermoplastic resin and silicone to a fiber cloth, thereafter subjecting said treated fiber cloth to irradiation by an ionizing radiation under heating; a process for preparing a fiber cloth incorporating a graft copolymer of silicone with thermosetting or thermoplastic resin characterized by applying the thermosetting or thermoplastic resin and silicone to a fiber cloth which has been dyed with a metal-containing dyestuff, thereafter subjecting said treated fiber cloth to irradiation by an ionizing radiation; and a process for preparing a fiber incorporating a graft copolymer of silicone with thermosetting or thermoplastic resin characterized by applying the thermosetting or thermoplastic resin and silicone to a fiber ing was 1.62 percent using 2.6 1O rad of total dose keeping at a irradiation temperature of 80 C. These data clearly show the increase in degree of grafting by the irradiation under heated condition. Also, No. 60 cotton broad cloth on which cloth which has been dyed with a metal-containing dyestuff, 5 silicone has been applied in an amount of 5 percent was exthereafter subjecting saidtreated fiber cloth to irradiation by posed to Co 60 -y-ray in the present of air at temperatures of an ionizing. radiation under heating. 50 C. and 80 C., thereafter drying was carried out for 5 hours It is apparent that all the fiber cloths, metal-containing at a temperature of 80 C. Cotton cloth thus treated was subdyestuff, silicone, thermosetting or thermoplastic resin, ir- 1 jected commercial drycleaning in many times and was tested radiation, etc. andthe operating conditions such as t'emperato determine the durability ofwater proofness in accordance ture, etc. mentioned previously can be applied tothis process. with ASTM test; D583-58 for water repellency. The results The finish of this invention can be applied to fiber, yarn, are tabulated below as Table 2: fabric, cloth and secondary productsthereof. Accordingly, the By the known process, spray test rating of water repellency invention includes any products produced by the processes of 15 decreased to 50 by 7 drycleanings even ifthe sample subjected this invention. 4.0Xl0 of total dose of irradiation. In contrast, the cloth TABLE 2 Irradiation Irradiation Number of dry-cleanings subjected (spray test rating) temperature total dose C (rad.) 0 1 2 a 4 5 6 7 s 9 10 '80 1.7X10 100 100 90 so N0'rE.Samples No. 7-10 are'shown for reference purposes only.

The invention is further described and illustrated by the following detailed examples.

EXAMPLE 1 1.5 g. ofNo. 60 cotton broad cloths on which silicone has been applied in an amount of 5 percent (silicone/fiber) was exposed to Co 60 'y-ray in the presence of air at temperatures of 50 C. and 80 C., thereafter the treated cloth was dried5 hours at a temperature of 80 C. The cloth thus treated was subjected to an extractionwith petroleum benzine as a solvent for 20 hours and rinsed sufficiently in methanol and water successively and dried: The weights of the measured cloths-were as follows:

recognized that by the process of this invention, the degree ofwater proofness of the treated cloth is significantly improved over that of the fabric treated with the prior art.

EXAMPLE-2 No. 60 cotton broad cloth was dyed using 0.6 percent and 2.0 percent of'Solar Rubinol B (a kind of copper complex salt of diazo dyestuff). Silicone was applied to the cloth thus TABLE 1 treated in anam'ount of 5 percent (silicone/fiberland the 233 Irradiation :52:33; Grafting cloth was subjected to irradiation of C0 y-ray in the temp. total dose grafting yield presence of air and dried 5 hours at C. The cloth thus 0 a sample No (ram (percent) (percent) treatedwassubjected to an extraction with petroleum benzine 80 1. 2X10: 0.75 15 50 for-20 hours andsuccessively rinsed sufficiently 'with'methanol 2g 2:2 3 and water and 'dried, Thereafter the weight of the cloth was 5 3 1. 2X18: 3% 51 measured and the'degree of grafting was calculated frorn the 50 i'gg 5 data; The results are tabulated in Table 3; As the controls, 55 1. 3&3: 8.2; f? nondyed cloth and the cloth dyed with Chryeamine G (a kind 138 55 of diazo dyestuff) were treated in the same manner and the 25 0 degree ofgraftingobtained are also tabulated'in Table 3.

TABLE 3 Cone. of Irradiation Degree ol Grafting Sample dyestutf total dose grafting yield number Dyestuff (percent) (rad) (percent) (percent) 2 52x10 4.!) 97 2 143x10 4.1 92 2 0.7X10'3 4.3 .l 0 1.!) 37 0.6 5.2)(10 4.0 98 0.6 1.3X10' 4,2 84 0.6 0.7)(10 4.2 84 0.6 0 0.1 2 2 4.7)(10G 0:7 13 i. 0.6 43x10 0.7 i3 11 Not dyed 0 4.7X 0.7 14 12 ..do 0 0 0 0 Sample Nos. 7-10 are shownfor reference purposes only.

By the known process, the degree of grafting was only 0.92 percent even though 4.0 l0 rad of total dose was used. in contrast, by the process of this invention, the degree of graft.-

Samples No. 9-l2 are given for reference purposes only.

EXAMPLES No. 60 cotton broad cloth'was dyed using 0.6 percent and'2 percent of Direct Fast Brown BRS (cupro triazo dyestuff).

The cloth thus dyed was treated as in Example 2. The results l melamine resin 411x10" are tabulated in Table 4. 2 melamine TABLE 4 Degree of Cone. of Irradiation silicone Grafting Sample dyestufl total dose grafting yield number Dyestuff (percent) (rad.) (percent) (percent) 13 Direct Fast Brown BBS... 2 5. 2X10 43 85 d0 2 0 0.1 2 ..d0. 0. 6 5. 2X10 4. 6 02 d0 0.6 1.3)( 0.0 18 10.. 0.6 0.7)(10 5.0 10 18 .d0 0.6 0 0.2 3

Example 4 No. 60 cotton broad cloth was dyed using 0.6% and 2% of Dlrect Fast Turquoise Blue (cupro phthalo cyanine dyestuff). The cloth thus dyed was treated as in Example 2. The results are tabulated in table 5.

TABLE 5 Irradiation Cone. of total dose Degree of Grafting Sample dyestuft of radiation grafting yield number Dyestuff (percent) (rad) (percent) (percent) 19". Digit Fast Turquoise Blue 2 4. 7X10 3.5 76 2 1.3x10 0.7 13 2 0.7X10" 0.4 7 2 0 0 O 0. 6 4. 7X10 1. 5 2.) 0.6 1.3)(10 0.4 8 0.6 0.7X10 0.3 5 0.6 0 0 0 EXAMPLE 5 3 ethylene urea 40x10" 1.15

resin To compare the degree of silicone grafting ofa cloth incor 4 ethylene um 0 porating a graft copolymer of silicone with some kinds of thermosetting resins and thermoplastic resins, No. 60 cotton 2 30x10 broad cloth (not finished), melamine resin, ethylene urea 7 acrylute resin 4mm" 1.40 resin, urea resin, and acrylate resin finished No. 60 cotton 3 W 0 a 010 broad cloth (each piece of cloth containing 5 percent of one 2 of said resins) was subjected to silicone treatment so as to incorporate 5 percent (silicone/fiber) silicone on the cloth. Each of these samples was divided into 2 portions, and one of which was further subjected Co 60 -y-ray in an amount of total close 4 1O rad. Thereafter, the thus treated cotton cloth was subjected to extraction with petroleum benzine for a predetermined number of hours and successively rinsed sufficiently with ethanol and water and dried. Then the weight of the samples was measured and degree of silicone grafting were calculated. The results are shown in table 6:

The sample No. 1,3, 5,7 and 9 are irradiated samples by yray and shows a higher degree of grafting than the corresponded samples of samples Nos. 2, 4, 6, 8 and 10 respectively. The degree of silicone grafting (3.25 percent) of the melamine finished cloth of sample No. l is especially high. Said degree of grafting is significantly higher than that obtained by non radiated sample No. 2 and by sample No. 9 which is a sample of silicone graft-only. Further. a number of commercial drycleanings were carried out on these finished TABLE 7 Number of dry-cleaning: spray Irradiation test rating Sample total dose No. Resin for pretreatment (rad.) U l 3 5 l0 l5 1... Melamine resin 4.0)(10 100 100 100 100 10 30 2 o 100 100 w s0 54) n 3 Ethylene urea resin. 4.0)(10 100 100 )0 s0 50 1| 4 d 0 100 no 70 0 n o 5 4.0x10 100 100 an 70 n n 6 no at) 0 0 n 0 T 4.0 10 100 no so 0 o n 8 d0 0 7o 0 0 0 0 1) cloths and after that durability of water proofness was measured in accordance with ASTM test; D583-58 for water repellency. The results are tabulated in table 7.

When samples Nos. 1 and 2 are compared, the superior ef- TABLE 6 feet produced by the y-ray irradiation on silicone melamine resin graft copolymerized cloth is clearly recognized in No. l. I R f l D Also, if the properties of product No. l are compared with a 6 em m mm 3' of those of No. 7, it is recognized that the properties of No. 1 are a pretreatment total dose silicone gmmng far superior to those of No. 7. Said superior properties are the (rad) a result of the melamine resin pretreatment. Sample No. 7 lacks such pretreatment.

' v EXAMPLE 6 Silicone was applied e as-55am SFTpeTEeFt GH- icone/fiber) to a No. 60 cotton broad cloth which had been dyed using 2 percent of Direct Fast Turquoise Blue GL (a kind of cupro phthalo cyanine dyestuff). The dyed cloth was subjected to the irradiation of Co 60 -y-ray in the presence of air heated to 75 C. Thereafter, it was dried at 80 C. for 5 hours. The thus treated cotton cloth was then subjected to an extraction with petroleum benzine and successively rinsed sufficiently with methanol and water and dried. The weight of the samples were measured. The results are tabulated in table 8. The effect of higher temperature is shown by comparing samples 2 and 4. ln sample 2 the degree of silicone grafting of dyed cloth with a total dose of 1.0X10 rad at 75 C. is 1.17 percent which is higher than the 0.7 percent of the sample 4 given a total dose of 1.3 M rad at 25 C. Also, in sample 2 the degree of silicone grafting of dyed cloth given a total dose of 1.0Xl rad at 75 C. is greater than that of the nondyed sample 6 given a total dose of 1.2Xl0 rad at 80 C. As previously stated, it is clear that the degree of silicone grafting increases, if irradiation is carried out under heating on a cloth dyed with metal-containing dyestuff.

Sample No. 4-7' are given for reference purposes only.

EXAMPLE 7 Silicone and melamine resin were applied in an amount of percent respectively to No. 60 cotton broad cloth. Said cloth was thereafter subjected to a irradiation of Co 60 y-ray in the presence of air at a temperature of 75 C., and dried for 5 hours at 80 C. Saidsamples were tested for durability of water proofness injaccordance with ASTM test D583-58 for water repellency. The results are given in table 9.

Using the durability of-water proofness obtained by the irradiation of 4.0 l0 rad at 25 C. as a standard, it is apparent that heating is useful since it makes it possible to attain the same degree of water proofness with a significantly smaller eelsqsssfi zs TABLE 9 Irradi- Number of dry-cleaning spray ation Irradiation test rating Sample temp. total dosage No. C.) (rad) 0 1 3 5 10 75 0. 7X10 100 100 100 100 80 80 76 1. 0X10 100 100 100 100 90 80 75 1. 5X10 100 100 100 100 90 80 0 100 100 90 80 25 4. 0X10 100 100 100 100 90 80 EXAMPLE 9 Silicone and melamine resin were applied in an amount of 5 percent respectively to No. 60 cotton broadcloth which had been dyed using 2 percent of Direct Fast Turquoise Blue GL (cupro phthalocyamne dyestuff). The cloth samples were subjected to irradiation of Co 60 'y-ray in the presence of air at a temperature of C. The treated samples were further heatedfor 5 hours at C., and thereafter dried at 80 C. for

- 5 hours/Said samples were tested for the durability of water TABLE 10 Irradi- Irradiation ation Times of dry-cleaning tempertotal spray test rating Sample ature dosage No. Resin C.) (Mrad.) 0 1 3 5 10 15 1 Melamin. 75 0.7 100 100 100 80 80 do 75 1.0 100 100 90 80 80 3 do 76 1.5 100 100 100 100 90 80 While in the foregoing specification this invention has been described in relation to preferred embodiments thereof, and many details have been set forth for the purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to other embodiments and that many of the details set forth herein can be varied considerably without departing from the basic principles of the invention.

What is claimed is:

1. In a process for preparing a silicone graft copolymerized fiber or cloth by copolymerizing silicone having a general formula of wherein R and R are hydrogen or alkyl radicals having up to five carbon atoms and R and R can be the same .or different,

7 and n is an integer, with a cloth having a molecular construction which can form free radicals within a molecule upon exposure to ionizing radiation, by irradiation of said silicone and said cloth, the improvement which comprises dyeing said cloth with a dyestuff containing metal in the form'of complex salt, then applying said silicone to the dyed cloth and subjecting said silicone coated dyed cloth to an ionizing radiation wherein the dosage of said ionizing radiation is within a range offrom 10" rad. to 10 rad.

2. A process as claimed in claim 1 wherein said cloth is cotton cloth.

3. A process as claimed in claim 1 wherein said irradiation is carried out at a temperature within a range from above room temperature but below the maximum temperature the cloth can withstand without destruction.

4. A process as claimed in claim 2 wherein said irradiation is carried out at a temperature within a range from room temperature to C.

5. A process as claimed in claim 1 wherein said cloth is selected from the groups consisting of rayon, cupra and acetate and said irradiation is carried out at a temperature up to 200 C. 

2. A process as claimed in claim 1 wherein said cloth is cotton cloth.
 3. A process as claimed in claim 1 wherein said irradiation is carried out at a temperature within a range from above room temperature but below the maximum temperature the cloth can withstand without destruction.
 4. A process as claimed in claim 2 wherein said irradiation is carried out at a temperature within a range from room temperature to 150* C.
 5. A process as claimed in claim 1 wherein said cloth is selected from the groups consisting of rayon, cupra and acetate and said irradiation is carried out at a temperature up to 200* C. 